WO2008059580A1

WO2008059580A1 - Thin film for use as reflective film or semi-transmissive reflective film, sputtering target and optical recording medium

Info

Publication number: WO2008059580A1
Application number: PCT/JP2006/322931
Authority: WO
Inventors: Tomokazu Obata; Hiroshi Yanagihara
Original assignee: Tanaka Kikinzoku Kogyo K.K.
Priority date: 2006-11-17
Filing date: 2006-11-17
Publication date: 2008-05-22
Also published as: EP2048524A4; US7910190B2; JPWO2008059580A1; CN101460873A; KR20090087052A; KR101279309B1; EP2048524B1; EP2048524A1; US20100040898A1; CN101460873B

Abstract

A thin film for use as reflective film or semi-transmissive reflective film, comprising a matrix of silver or silver alloy and, dispersed therein, a phase of at least one compound selected from among gallium, palladium and copper nitrides, oxides, composite oxides, nitroxides, carbides, sulfides, chlorides, silicides, fluorides, borides, hydrides, phosphides, selenides and tellurides. The compound phase of the thin film may contain, as well as the above compounds, at least one compound selected from among silver nitride, oxide, composite oxide, nitroxide, carbide, sulfide, chloride, silicide, fluoride, boride, hydride, phosphide, selenide and telluride. This thin film reduces drop of reflectance in the long-term use, thus attaining prolongation of the life span of optical recording medium, display and other various apparatuses using the reflective film. This thin film is also useful as a semi-reflective/semi-transmissive film for use in optical recording medium.

Description

Specification

Thin film and sputtering target for reflective film or semi-transmissive reflective film, and optical recording medium

Technical field

[0001] The present invention relates to a thin film useful as a reflective film or a transflective film used in an optical recording medium, a display, or the like. In particular, the present invention relates to a thin film in which a decrease in reflectance is suppressed even after long-term use and an optical recording medium including the thin film as a reflective film or a semi-transmissive reflective film. Background art

[0002] Optical recording media such as CD-R / RW, DVD-R / RW / RAM, and Blue-Ray discs, and display devices such as liquid crystal displays and organic light-emitting displays have at least one reflective film. For example, Fig. 1 shows the structure of an HD-DVD (rewritable single-sided double layer) that has been developed recently as an example of an optical recording medium. As shown in this example, the optical recording medium has a multilayer structure including a reflective film in addition to a protective layer and a thermal diffusion layer in addition to a recording layer that plays a central role in its function.

[0003] Many conventional reflective films also have silver strength. Silver is less expensive than gold, which has high reflectivity and also has high reflectivity. In addition, silver has excellent light transmittance by adjusting its film thickness appropriately, so it can be applied as a transflective film, and it can be applied to future optical recording media. (See Figure 1).

[0004] On the other hand, silver has a problem that it changes its color to black due to corrosion having poor corrosion resistance and lowers reflectance. The reason for the corrosion of the reflective film varies depending on the medium and the device to be applied. For example, it is corroded by the organic dye material applied in the recording layer of the optical recording medium, and the reflectance decreases due to long-term use. It is done. In addition, the reflective film of the display device may be corroded due to atmospheric humidity or the like. Therefore, in order to solve the problem of corrosion resistance of silver, a thin film having a silver alloy power obtained by adding various elements to silver has been developed.

[0005] For example, in Patent Document 1, 0.5 to 10 atomic% of ruthenium and 0.1 to 10 atomic% of aluminum are added to silver. In Patent Document 2, 0.5 to 4.9 are added to silver. and a film obtained by adding a Palladium © beam of atoms ^_0/0 is disclosed. In Patent Document 3 and Patent Document 4, Ag is C. Disclosed are a, V, and Nb.

Patent Document 1: Japanese Patent Laid-Open No. 11 134715

Patent Document 2: JP 2000-109943

Patent Document 3: Japanese Patent Laid-Open No. 6-243509

Patent Document 4: Japanese Patent Laid-Open No. 2003 6926

Disclosure of the invention

Problems to be solved by the invention

[0006] The thin film composed of the above silver alloy has a certain effect in improving the corrosion resistance. However, although the corrosion problem should have been solved, even an optical recording medium using a silver alloy thin film cannot completely suppress a recording error due to deterioration of the reflective film. In addition, with future demands for further improvements in recording speed and recording density, materials with better reflectance maintenance characteristics than ever are required.

[0007] Therefore, the present invention is a thin film applied to a reflective film and a semi-transmissive reflective film constituting an optical recording medium, a display, etc., and can function without lowering the reflectance even after long-term use. An object is to provide what can be performed and a method for manufacturing the same.

Means for solving the problem

[0008] The inventors of the present invention, which should solve this problem, have intensively studied and studied the poor mechanism of reflection characteristics of the silver thin film, and the cause is not only simple corrosion (blackening) but also during heating. It is said that there is also a movement phenomenon of silver atoms. This silver atom movement phenomenon is a phenomenon in which a flat thin film immediately after film formation moves as the silver atoms constituting the thin film become very stable in terms of energy depending on the added environmental conditions. is there. And the movement of silver atoms at this time is not necessarily flat, but often takes three-dimensional behavior, and as a result, aggregates in a polygon close to a sphere. When a three-dimensional aggregate formed on the thin film is formed, the reflected light of the laser light incident on the thin film is diffusely reflected in the direction of the incident axis and reflected in multiple directions. Therefore, in an optical recording medium using such a thin film as a reflection film, the reflectance of the optical recording apparatus in the sensor axis direction is reduced, which causes an error in the recording medium.

[0009] The migration phenomenon and aggregation of silver atoms as described above are phenomena different from corrosion. In this respect, conventional silver alloys do not have any inhibitory effect on the migration phenomenon of silver atoms. It is not considered. This is because metal atoms alloyed with silver are considered to have some effect of blocking the movement of silver atoms. However, since the conventional silver alloys were exclusively aimed at improving the corrosion resistance and the like, it can be said that all alloying was effective in suppressing the migration of silver atoms.

[0010] Therefore, the present inventors examined a technique for suppressing the movement of silver atoms in the thin film, and studied a silver alloy having the effect. As a further improvement, it is effective to disperse the compound phase in silver or a silver alloy by suppressing the movement of silver atoms, thereby making it possible to obtain a thin film having excellent reflectance maintenance characteristics. The inventor came up with the present invention.

[0011] That is, the present invention provides a matrix having silver or silver alloy strength with gallium, palladium, copper nitride, oxide, composite oxide, nitride oxide, carbide, sulfide, chloride, silicide, fluoride. A thin film for a reflective film or semi-transmissive reflective film in which a compound phase comprising at least one of a compound, boride, hydride, phosphorous, selenium, and telluride is dispersed.

[0012] In the present invention, the phase of the compound force of the above three metals is dispersed in the matrix of silver or silver alloy force, so that the movement of silver atoms constituting the matrix is inhibited, and the planarity of the thin film is improved. Can be maintained. As a result, even if the thin film is subjected to heat, a decrease in reflectance is suppressed.

[0013] Table 1 shows specific examples of the compound phase. These compounds include, as shown in Table 1, a stable stoichiometrically balanced compound composition, as well as stoichiometrically non-equilibrium compounds such as GaN (gallium nitride). ) Includes Ga N (0 <X <1).

[0014] [Table 1] Ga Cu Pd Nitride GaN (Ga, — _X N _X ) Cu ₃ N (Cu ₃ - _Z N _Z ) PdN (Ρφ_ _χ _{χ χ} ) Oxide Ga ₂ 0 ₃ (Ga _{1 5} _ _a O,) Cu ₂ 0 (Cu _z _yO _y ) PdO (Pd ,. _x O _x ) Hydride CuC (Cu ^ Cx) PdC (Pd 卜_X C _X ) Sulfide CuS (Cu ^ S PdS (Ρφ— _X S _X ) Fluoride GaF ( G _ai . _X F _x ) CuF ₂ (Cu _y 0 ₂ _y) PdF (Pd ^ Fx)

W Compound GaB (Ga ^ B CuB (Cu xBx) PdB (PdnBj σ

Silicide GaO C mS ϋt (Ga— _x Si _x ) Cu ₅ Si (Cu _5. _b O _b ) PdSi (Pd 卜_x Si _x ) Chloride GaCI ₃ (σGa _x CI _3. _x ) CuCI (Cu, — _X CI _X ) PdCI ₂ (Pd _y B ₂ ) Phosphide GaP (Ga ^ Pj CuP (C _Ul . _X P _x ) PdP (Ρφ- _χ Ρ _χ ) ϋ

Selenide GaSe (Ga ^ Se,) CuSe (Ci ^ — _x Se _x ) PdSe (Ρφ— _x Se _x ) Telluride GaTe (Ga ^ Te CuTe (Cu'-xTeJ PdTe (Ρφ— _x Te _x )

CuGaS ₂ , AgGaS ₂ CuFe ₂ 0 ₄ , CuMo0 ₄

Complex oxide CuGaSe ₂ , AgGaSe ₂ GuTi0 ₃ , CuCr ₂ 0 ₄

_{_{_{CuGaTe 2, AgGaTe 2 CuW0 4,}}} CuSe0 4

0 <x <1, 0 <y <2, 0 <z <30> a <1.5, 0 <b <5

[0015] Further, the thin film according to the present invention comprises silver nitride, oxide, composite oxide, nitride oxide, carbide, sulfide, chloride, silicide, fluoride, boride, hydride, phosphorus. It is also possible to include any silver compound in the compound, selenium compound, or telluride compound as the compound phase. Specific examples of this silver compound are shown in Table 2. This silver compound includes those formed at the same time as the formation of the compound phase such as gallium in the thin film manufacturing method described later, in addition to those formed intentionally. The compound phase which is a composite force of silver has the effect of suppressing the movement of silver atoms in the thin film, like the compound phase such as gallium. Note that these silver compound phases also include stoichiometrically non-equilibrium compounds.

[0016] [Table 2]

Nitride _{_{_{AgN (A gl _ x N x}}} )

Oxide Ag ₂ 0, AgO (A — _x O _x )

Carbide AgC (Ag 卜_X C _X )

Sulfide Ag ₂ S (Ag ₂ _ _x S _x )

Fluoride AgF (Ag—xFj

OR compound AgB (Ag'—χΒχ)

Silicide AgSi (Ag, — _x Si _x )

Chloride AgCI (A & — _X CI _X )

Phosphoride AgP (A & — _X P _X )

Selenide _{_{_{Ag 2 Se (Ag 2 -ySe y}}} )

Telluride Ag ₂ Te (Ag ₂ -yTe _y )

Ag ₂ 0 ₄ Ag ₂ W0 ₄

Composite oxide AgV0 ₃ Ag ₂ Cr0 ₄

Ag4P2 07 Ag3P04

0 <x <1, 0 <y <2

[0017] The content of these compound phases is preferably 0.001-2. 5% by weight. In order to sufficiently prevent silver atom migration, a compound phase of 0.001% by weight or more is necessary. Also, the upper limit is 2.5% by weight because if it exceeds this, the initial reflectivity of the thin film becomes insufficient. The content of the compound phase is more preferably 0.001 to 1.0% by weight, and still more preferably 0.001 to 0.5% by weight. When the content of the compound phase increases, the effect of suppressing the decrease in reflectivity increases, but the reflectivity tends to decrease. The content of the compound phase is preferably adjusted within the above range depending on the application. The content of the above compound phase is based on the weight of the entire thin film (total weight of the matrix and the compound phase). Further, when a silver compound phase is present, it is the sum of the content of the silver compound and the content of the gallium, noradium, and copper compounds. Furthermore, even when only a compound of gallium, noradium, and copper is present as the compound phase, the content is preferably within the above range.

[0018] The compound phase may be dispersed in a particle state composed of a large number of compound molecules, but is not necessarily limited to this form. That is, the compound phase may consist of at least one compound molecule. The size of the compound phase is preferably not more than lZio of the thickness of the thin film. For example, if the thickness of the thin film is 1000 A, a compound phase of 10 OA or less is preferred. It is preferable to disperse.

On the other hand, the matrix of the thin film according to the present invention is pure silver or a silver alloy.

In the present invention, the effect of suppressing silver atom migration is mainly possessed by the compound phase, but the effect of alloying cannot be ignored. Moreover, even if pure silver is used as a matrix, the thin film has excellent reflectivity maintaining characteristics due to the action of the compound phase. Therefore, pure silver and silver alloys are used as a matrix.

[0020] When the matrix is a silver alloy, the alloy is preferably an alloy of silver and at least one element of gallium, nor << radium, or copper. These elements are the metal elements constituting the first compound phase mentioned above, but the movement of silver atoms can also be suppressed by alloying with silver.

[0021] When the matrix is a silver alloy, the concentration of the metal alloyed with silver is preferably 0.01 to: LO wt%. If less than 0.01% by weight, the meaning of alloying is negligible. The concentration is more preferably 0.01 to 5% by weight, and still more preferably 0.01 to 3.5% by weight. The metal concentration here is based on the weight of the silver alloy that is the matrix.

Next, a method for manufacturing a thin film according to the present invention will be described. The reflective film according to the present invention preferably has a thickness of 120 A to 1200 A when applied to an optical recording medium, a display or the like. As a method for producing such a thin film, sputtering is preferably applied. When applying the sputtering method to the production of a thin film containing a compound phase, there are the following two directions.

[0023] The first method is to apply a target approximated to the structure and configuration of a thin film to be manufactured, that is, a matrix made of silver or a silver alloy, gallium, palladium, copper nitride, oxide, composite acid. A compound phase consisting of at least one of yttrium oxide, nitride oxide, carbide, sulfide, chloride, silicide, fluoride, boride, hydride, phosphide, selenium oxide, tellurium oxide is dispersed. This method uses a sputtering target. According to this method, since a thin film can be manufactured with one target, it is possible to perform sputtering in a manner in which the target and the substrate face each other, which is usually performed in the production of a reflective film. Property is improved. Here, as a sputtering target for manufacturing a thin film according to the present invention, the following three There is a form.

[0024] First, an internal compound target. An internal compound target is a material made of silver (pure silver) or silver alloy that is heat-treated in an atmosphere of high-pressure oxygen gas, nitrogen gas, etc., and a metal that forms an alloy with silver or silver inside the target material. Partially combined with oxide, nitride, etc. In addition, although the raw material raw material here may be a plate-like thing close to the shape of the target, it may also be compression-molded after being internally combined as a granular material.

[0025] Alternatively, a sintered target may be used. The sintered target is obtained by mixing silver (pure silver) or a silver alloy powder and a powder composed of a compound to be dispersed in accordance with a target composition, compression-molding, and sintering. This sintered target is useful when it is difficult to produce the compound phase, such as when the concentration of the compound phase is limited in the above-mentioned internal compound type. For example, as the compound phase, copper oxide, gallium oxide, nitride It is suitable for manufacturing a thin film in which copper is dispersed.

[0026] Further, it is an embedded target. An embedded target is a target made of pure silver or a silver alloy, and a small piece (columnar shape, spherical shape, etc., which is not limited to a shape) that has a compound power to be dispersed is embedded in the consumable region of sputtering. is there. The above-mentioned internal compound target and sintered target have a composition and structure close to a thin film to be manufactured microscopically as shown in Fig. 2 (a), whereas this target is shown in Fig. 2 (b). Thus, it is close to a thin film for manufacturing purposes in a macro manner. In this target, the composition of the thin film to be manufactured can be controlled by the diameter, the arrangement position, the number of the embedded compound pieces, and the sputtering rate.

[0027] In the above three types of targets, the content of the compound phase is preferably the same as that of the thin film for production. Therefore, the content of the compound is 0.5 001-2. 5 wt% is rather preferred, from 0.001 to 1.0 preferably than the weight ^_0/0 force, from 0.001 to 0.5 wt ^_0/0 force further I like it! In addition, the size of the compound phase of these targets may be at the molecular level as in the case of a thin film intended for production without particular limitation, or may be on the order of mm as in the case of embedded targets. This is because, regardless of the size of the compound phase, during sputtering, the compound is sputtered in molecular units to form a thin film having the desired composition.

[0028] Further, since this target preferably has the same configuration as the thin film for manufacturing purposes, the silver alloy serving as the matrix is at least one of silver, gallium, noradium, and copper. Alloys with power 1 elements are preferred. The concentration of alloy metal such as gallium is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, and still more preferably 0.01 to 3.5% by weight.

[0029] The second directionality for producing the thin film according to the present invention is to improve the sputtering method. In this method, the target mainly used is a general pure silver target or a silver alloy target, and does not use a special target such as the first direction. In the second direction, the following two methods can be applied.

[0030] First, simultaneous sputtering using a plurality of targets. This is a method in which sputtering is simultaneously performed using a plurality of targets having the same composition as the phases constituting the thin film and a metal force. For example, pure silver target or silver alloy target and gallium oxide (Ga

2

O) Use two targets of the target and put them together in the chamber

3 A thin film in which a compound phase that also has an oxygallium force is dispersed in silver or a silver alloy can be manufactured by arranging them in one and performing sputtering at the same time. This method is useful when it is difficult to manufacture a special target such as the above-described internal compound target.

[0031] Further, in this second direction, the application of reactive sputtering is particularly useful. Reactive sputtering is a method in which a reactive gas such as oxygen or nitrogen is added to the sputtering atmosphere to perform sputtering, and all or part of the sputtered particles from the target are oxidized and nitrided to form a thin film. . Reactive sputtering is a useful method when the compound to be dispersed in the thin film is expensive, difficult to obtain, or difficult to produce chemically.

[0032] This reactive sputtering may be applied singly or in combination with other methods. For example, when using the above-mentioned special integrated target, that is, when using an internal compound target, a sintered target, and an embedded target, it is predicted that the compound content will be insufficient if these targets are used alone. In this case, the content of the compound can be increased by introducing a reactive gas into the atmosphere. Also, in the production of thin films by simultaneous sputtering, the amount of compound can be adjusted by combining reactive sputtering. Brief Description of Drawings

FIG. 1 is a diagram showing an example of the structure of an HD-DVD.

FIG. 2 is a view showing a specific example of a sputtering target for producing a reflective film and a transflective film according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0034] In this embodiment, first, three types of targets of an internal compounding type, a sintered type, and an embedded type were manufactured. In addition to the production of thin films using these targets, thin films were produced by the simultaneous sputtering method and the reactive sputtering method. In the following explanation, when the composition of the target and the thin film is expressed, the front part of “Z” is the matrix and the rear part is the compound phase as in the matrix Z compound phase. Further, the alloy element concentration when the matrix is a silver alloy indicates the weight percentage in the silver alloy that is the matrix. For example, Ag-10.Owt% Ga / l.Owt% CuN in Sample No. 10 is the Ag-10.Owt% Ga group.

Three

This shows a thin film (target) in which 1.0% by weight of Cu N is dispersed based on the total weight of the thin film (target).

Three

[0035] A: Production of sputtering target

(a) Internal compound target

Particle size 1.0 to 3. Omm granular Ag— 2. Prepare Owt% Ga alloy raw material 5. Okg, put it in a high pressure reaction kettle, thoroughly replace the inside of the kettle with nitrogen gas, Gas pressure was increased to 0.8 MPa and the temperature was increased to 800 ° C, and the temperature was raised and held for 48 hours to internally nitride Ga. Then, after slow cooling, it was taken out, loaded into a mold, and subjected to high-pressure extrusion at 750 ° C. for integral molding. After forming, it was forged and rolled into a plate material (dimensions: 160mm X 160mm X 6mm). This was then cut into a standard sputtering target (diameter 152 mm (6 inches), thickness 5 mm). The composition of this target is AgZ2.5 wt% GaN with silver as a matrix and 2.5 wt% gallium nitride as a composite phase, and corresponds to Sample No. 1 described later.

[0036] In addition to the above, Ag / 1.0 wt% Cu3N (Sample No. 2) was manufactured as an internal compound target. The sample No. 2 target was internally nitrided using an Ag-0.93 wt% Cu alloy as a raw material and a nitrogen gas pressure of 0.5 MPa, a temperature of 750 ° C., and a holding time of 24 hours. [0037] (b) Sintered target

In each case, Ag— 10. Owt% Ga alloy powder and copper nitride powder with a particle size of 50 ~: LOO μm are prepared, weighed to the desired composition, mixed well, and then put into a carbon mold. After filling and compression, it was integrated in a vacuum sintering furnace by sintering at 750 ° C for 8 hours. After sintering, forging and rolling were performed in order to further improve the density, cutting was performed to obtain a sputtering target having the same standard dimensions as described above. The composition of this target is Ag—10.0 wt% Ga / l. Owt% Cu N, which corresponds to Sample No. 10 described later.

Three

As the sintered target, silver alloy powder and compound powder were changed, and in addition to the above, targets corresponding to Sample Nos. 3 to 9, 11, and 12 were produced.

[0038] (c) Embedded target

Prepare a disc made of Ag— 3. Owt% Ga—0.5 wt% Cu alloy of standard dimensions (diameter 152 mm (6 inches), thickness 5 mm), with a diameter of 1 in the circumference of 80 mm diameter. A 05mm round hole is drilled at three equal intervals, and this round hole has a diameter of 1. Omm and a length of 5mm.

twenty three

) I inserted a round bar that was also powerful. In order to prevent the round bar from falling off, the peripheral force was also applied to fix the round bar to make an embedded target. The composition of this target is equivalent to Ag-3. Owt% Ga-0.5Cuwt% / l.Owt% GaO and corresponds to sample No. 13 described later.

twenty three

To do.

For embedded targets, in addition to the above, change the alloy composition of the disc and the composition and number of the embedded round bars to produce targets corresponding to sample Nos. 14 to 19 in addition to the above. did.

[0039] B: Production of thin film

Thin films were produced using the above-mentioned various targets and applying the co-sputtering method and the reactive sputtering method. Here, a thin film was produced on a polycarbonate substrate for DVD. This substrate is produced by an injection molding machine to obtain Bei the stamper preformat 'pattern is formed (diameter 120 mm, thickness 0. 6 mm) ₀ On the upper surface of the substrate, reflected by the method A film was formed with a thickness of 120A.

[0040] (i) A thin film was formed on a polycarbonate substrate using the three types of targets produced in (a) to (c) above. After setting each target in the sputtering chamber and evacuating, Ar The gas was introduced until 5.0 X ^10_1 Pa. Then, the substrate position was set to a stationary state immediately below the target, and sputtering was performed at a DC of 0.4 kW for 8 seconds. The film thickness distribution is within ± 10%.

(ii) Co-sputtering

Ag- 1. Owt% Pd- l. Silver alloy target with Owt% Cu composition, commercially available gallium oxide target, and three targets of palladium oxide target are concentric with a 160mm radius from the central axis of the sputtering equipment. It was set at the position divided into three. After evacuating the inside of the apparatus, Ar gas was introduced until 5. OX 10 ^{_ 1} Pa. After that, the substrate is placed on the center of the turntable and rotated at lOrpm, while the silver alloy target has a direct current of 0.99kW, the gallium oxide target has a high frequency of 0.1 lkW, and the acid / palladium target has a high frequency of 0.03kW. Sputtering power was applied and sputtering was performed for 8 seconds. The composition of the thin film produced here is: Ag— 1. Owt% Pd- l. Owt% Cu / 0. Lwt% Ga O—0. Lwt% Pd

twenty three

O, corresponding to Sample No. 23 described later. In this simultaneous sputtering, the composition of the thin film can be adjusted by changing the type of silver alloy target and the type of target combined therewith. In this embodiment, the thin films of Sample Nos. 20 to 22 and 24-43 are also used in this method. Manufactured with.

(iii) Reactive sputtering

Ag—0.8wt% Ga- l. A silver alloy target with a composition of 0wt% Cu and a silver alloy target with an composition of Ag—1.0wt% Ga—1.0wt% Cu are set in a sputtering system. After evacuation, Ar gas was introduced until 5. OX 10 ^_1 Pa. Thereafter, nitrogen gas was introduced as a reactive gas. The partial pressure of nitrogen gas was 2.0 ^{× 10_3} Pa. Then, while placing the substrate on the center of the turntable and rotating at lOrpm, sputtering was applied for 8 seconds by applying a sputtering power of DC 0.5kW to each target. The composition of the thin film produced here is Ag—0.8 wt% Ga-l. 0 wt% Cu / 0.1 wt% GaN, which corresponds to Sample No. 48 described later. In reactive sputtering, the composition of the thin film can be adjusted by increasing or decreasing the type of target, the partial pressure of the reactive gas, and the sputtering power when using two or more targets. 47, 49-117 thin films were produced by this method.

C: Evaluation of thin film A thin film formed on a polycarbonate substrate as described above was used as a DVD medium, and the thin film was evaluated by evaluating its characteristics. The evaluation is performed on an optical disk evaluation device (Pulstec Industrial Optical Disk Evaluation Device ODU-1000), and the jitter value, PI error, PO failure, and reflectance in the initial state after manufacture are measured, and these are within the DVD standard range. It was confirmed that

[0042] Next, an accelerated environmental test was performed in which the DVD medium was exposed to an environment of temperature 80 ° C and relative humidity 85% for 500 hours. The DVD media after the accelerated environmental test were evaluated using the evaluation device. Was measured. The results are shown in Tables 3-6. The table also shows the results of similar tests on DVD media with pure silver as the reflective film.

[0043] [Table 3]

* 1 The front part of J indicates silver or a silver alloy as a matrix, and the rear part indicates a compound phase.

* 2 Thin M

a: Uses inner city compound target

b: Uses a sintered target

o: Use embedded target

[0044] [Table 4] Specimen PO: Ra PO Feire Jitter (¾) S Shooting W

No. Sample composition (wtW) * ¹

Manufacturing method Initial after humidification Initial after humidification Initial after humidification Initial after humidification

20 A £ -2.5Ga-1.0Cu / 0.5GaN d 37.7 1212.2 0.0 6.5 6.4 21.3 49.5 49.3

21 Ag-3.0Ga-1.0Pd-1.0Cu /Z.5Cu3N d 28.1 881.5 0.0 4.3 6.9 19.2 48.1 46.5

22 Ag-3.0Ga-1.0Pd-1.0Cu /I.OCuO d 11.3 1128.4 0.0 5.2 7.2 20.7 48.7 48.6

Ag-1.0Pd-1.0Cu /

23 d 43.0 666.0 0.0 3.6 6.8 14.3 52.6 52.5 0.1Ga2O3-0.1PdO

24 As / 2.5Cu2S d 45.3 1346.8 0.0 7.4 6.2 22.7 52.2 52.4

25 Ag-1.0Cu / 0.1Cu2S d 18.4 1346.8 0.0 7.4 7.5 23.8 53.2 53.3

26 A £ r1.0Ga / 0.1Cu2S d 42.2 1313.5 0.0 7.1 7.2 22.3 53.3 53.0

27 Ag-1.0Cu-0.8Ga / 0.1 Cu2S d 12.1 1262.9 0.0 7.3 7.4 23.4 52.0 50.6

28 Ag-1.0Pd / 0.1Cu2S d 18.1 1310.4 0.0 7.2 6.7 23.8 53.6 51.9

29 AfiH .0Cu-1.OPd / 0.1 Cu2S d 42.7 1199.3 0.0 6.7 6.2 21.1 51.7 50.8

30 Ar-1.5Ga-2.0Cu / 2.5PdSi d 14.7 760.0 0.0 3.8 6.6 14.9 49.9 49.9

31 Agr3.0Ga-0.5Pd / 1.OPdSi d 18.2 1031.4 0.0 5.4 6.3 17.9 49.3 47.9

32 Ag / 2.5PdSi d 30.5 636.0 0.0 3.0 6.7 13.5 51.8 50.7

33 Ag-3.5Pd / 0.1PdSi d 41.6 820.0 0.0 4.1 6.5 14.9 51.1 49.7

34 Ag-1.0Ga / 0.1PdSi d 45.3 826.8 0.0 3.9 6.4 14.6 53.1 52.3

35 A ^ 1.0Cu-0.8Ga / 0.1PdSi d 47.0 805.6 0.0 3.8 6.9 15.0 52.2 51.6

36 Ag-1.0Pd / 0.1PdSi d 23.0 812.0 0.0 4.0 7.6 15.7 53.3 53.5

37 Ag-1.0Cu-1.OPd / 0.1 PdSi d 43.4 630.4 0.0 3.2 6.8 13.9 52.3 52.3

38 Ag / 0.5Cu3P d 32.9 1160.0 0.0 5.8 7.1 20.9 49.2 49.0

39 Ag 0.5Cu2S d 17.3 240.0 0.0 6.2 7.0 1Θ.9 50.7 50.3

40 Ag 0.5Cu5Si d 38.5 1047.6 0.0 5.4 6.6 18.4 49.6 49.3

41 Ag / 0.5Cu2Se d 20.2 970.0 0.0 5.0 6.6 18.9 49.6 49.2

42 Ag 0.5Cu2Te d 21.2 1128.6 0.0 5.4 6.3 18.9 48.7 48.8

43 Ag 0.5CuCI2 d 39.1 1067.0 0.0 5.5 7.2 19.0 49.0 48.9

AglOO.0 1 41.4 1664.0 0.0 8.0 7.6 27.0 56.8 51.7

* 1 Before Γ / J »Minute is matrix« or silver alloy, rear part is compound phase

* 2 For the manufacturing method

a: Use internal β-compound target

b: Uses a sintered target

c: Use embedded target

d: Simultaneous sputtering

e: Reactive sputtering 5]

* 1 The front part of Γ / J indicates the silver or silver alloy that is the matrix, and the rear part indicates the compound phase.

* 2 Regarding the thin belly manufacturing method,

a: Use inner »compound target

b: Uses baked β-type target

ο: Use embedded target

d: Simultaneous sputtering

β: Reactive sputtering Table 6] "HIT PI error"

耝料成成 (wt 6 I 1 PO Fae J ”Jitter) _ S shooting (I

No. ¹ * ' ^{1 i}

82 Ar-O.eGa-1.OCu / 0.1 Ga203 e 22.6 633.0 0.0 5.4 6.2 18.3 50.5 49.7

83 Ag-1.0Ga-1.0Cu / 0.1 Ga203 e 20.5 506.7 0.0 5.1 6.8 18.6 52.9 53.1

84 Ag-0.4Ga-1.0Cu / 0.2Ga2O3 e 20.6 812.6 0.0 4.4 6.9 15.8 53.1 53.1

85 Ag-0.6Ga-1.0Cu / 0.2Ga2O3 e 39.4 745.9 0.0 5.7 6.5 19.1 50.6 49.3

Ag-0.BGa-1.0Cu /

86 e 22.1 651.4 0.0 4.5 6.8 16.1 49.4 49.5 0.2Ga2O3-0.4Cu2O

87 Ag-0.4Ga-1.0Cu / 0.3Ga2O3 e 47.2 951.0 0.0 5.2 7.4 18.9 51.9 51.3

8B Ag-0.8Ga-0.1 Pd-1.0Cu / 0.1 GaN e 38.0 717.6 0.0 3.9 7.4 14.9 50.7 50.3

89 Ag-0.eGa-0.2Pd-1.0Cu / 0.2GaN e 13.1 849.1 0.0 4.6 7.6 16.8 50.7 49.5

90 Ag / 2.5Cu3N e 41.4 1320.0 0.0 7.5 6.2 22.0 51.7 51.9

91 Ae-T-0Cu / 0.1Cu3N e 41.2 1161.6 0.0 6.6 6.5 20.5 53.4 52.8

92 Ag-1.0Ga / 0.1Cu3N e 39.5 679.0 0.0 3.5 7.1 15.7 52.9 52.6

93 Ag-1.OCu-0.8Ga / 0.1Cu3N e 36.3 554.9 0.0 3.1 6.6 13.3 52.5 51.8

94 Ag-1.0Pd / 0.1Cu3N e 14.3 1047.6 0.0 5.4 6.9 19.4 53.4 52.5

95 Ag-1.0Cu-1.0Pd / 0.1Cu3N e 34.7 680.6 0.0 2.2 7.4 12.7 51.8 51.9

96 Ag-1.0Ga-1.0Pd / 0.5Cu3N e 46.3 1319.9 0.0 6.7 7.5 23.4 50.6 49.7

97 Ag 2.5CuO e 32.3 1324.6 0.0 7.4 6.2 22.9 52.1 52.3

98 Ag-1.0Cu / 0.1CuO e 47.2 1401.4 0.0 7.7 7.4 26.6 53.3 52.5

99 Ag-1.0Ga / 0.1CuO e 43.3 1353.6 0.0 7.2 6.5 21.5 52.7 52.3

100 Ag-1.0Cu-0.8Ga / 0.1GuO e 30.1 1280.5 0.0 6.5 7.0 22.5 52.2 51.6

101 Ag-1.0Pd / 0.1CuO e 48.3 1262.9 0.0 7.3 7.3 25.4 53.2 53.1

102 Ag-1.0Cu-1.0Pd / 0.1CuO e 33.6 1337.0 0.0 7.0 6.1 22.7 52.3 51.6

103 Ag-1.0Ga-1.0Pd / 0.5CuO e 36.6 1337.6 0.0 6.4 6.4 19.4 50.0 49.6

104 Ag 2.5PdO e 11.8 636.0 0.0 3.0 7.3 14.0 49.3 4Β.8

105 Ag-3.5Pd / 0.1PdO e 40.6 451.5 0.0 1.9 7.6 11.8 49.5 48.7

106 Ag-1.0Ga / 0.1PdO e 33.7 343.8 0.0 1.8 6.7 11.1 51.2 50.1

107 A ^ 1.0Cu-0.8Ga / 0.1PdO e 21.6 355.3 0.0 1.7 6.6 10.2 50.2 50.4

108 Ag-1.0Pd / 0.1PdO e 33.3 477.5 0.0 2.5 7.3 13.1 51.5 51.5

109 A ^ 1.0Cu-1.0Pd / 0.1PdO e 25.9 401.1 0.0 2.1 6.5 10.8 50.4 48.8

Ag-O.8Ga-1.0Cu /

110 e 31.2 373.3 0.0 3.7 7.6 15.5 49.8 49.5 0.01GaN-0.02Cu3N

Ag-0.8Ga-1.OCu /

111 e 39.6 349.3 0.0 3.4 6.7 15.0 51.θ 50.4 0.1 GaN-0.2Cu3N-0.01Ag

Ag-0.8Ga-1.0Cu /

112 e 40.1 436.5 0.0 2.9 7.5 13.4 51.7 51.9 0.01Ga2O3-0.02Cu2O

Ag-0.8Ga-1.0Cu /

113 e 49.1 431.9 0.0 2.7 € .2 12.5 50.6 48.9 0. Ga2O3-0.2Cu2O-0.01 Ag20

114 Ag-l.0Pd-1.0Cu / 0.0t Cu3N e 45.7 610.7 0.0 3.1 7.3 15,0 51.7 51.0

Afi-1.0Pd-1.0Cu /

115 e 14.7 585.2 0.0 2.8 6.5 12.9 51.1

0.1Cu3N-0.01AgN 50.6

Ag-1.0Pd-1.0Cu /

116 e 48.8 424.0 0.0 2.0 6.6 10.6 52.2 51.3 0.01PdO-0.02Cu2O

Ag-1.0Pd-1.0Cu /

117 e 17.9 465.6 0.0 2.4 6.4 11.4 50.5 50.7 0.1 PdO-0.2Cu2O-0.01 AgO

Ag100.0 1 41.4 1664.0 0.0 8.0 7.6 27.0 56.8 51.7

* ι r / j indicates the matrix silver or silver alloy, and the back part indicates the compound phase

* 2 For the calf production method, see below.

a: Within »Use compound target

b: Uses a sintered target

c: Use embedded target

d: Simultaneous sputtering

e: Reactive sputtering As can be seen from these tables, the recording medium provided with the reflective film having the compound phase according to the present invention has more PI errors and PO failures than the DVD medium using the pure silver as the reflective film. Furthermore, it was confirmed that the rate of decrease in reflectance was low. DVD media with a pure silver reflective film After the humidification test, the body was not recognized by the recording device and became unusable. Industrial applicability

[0048] As described above, the thin film according to the present invention can prolong the lifetime of various devices to which a reflective film such as an optical recording medium or a display whose decrease in reflectance is small even after long-term use. Further, the reflectance maintenance characteristic of the reflective film according to the present invention is hardly affected by the wavelength of incident light. In this regard, in the field of optical recording media, the wavelength of recording light sources has been shortened, such as the development of HD-D VD using a blue laser. The present invention can also cope with such a technique. For example, when applied to an optical recording medium, there are advantages of reducing the number of errors and increasing the life.

[0049] In the present invention, the reflective film is sufficient if it has a function of reflecting light, and includes a film having light transmittance. Therefore, it is possible to cope with a semi-reflective / semi-transmissive film applied in an optical recording medium.

Claims

The scope of the claims

[I] In the matrix that also has silver or silver alloy strength, gallium, noradium, copper nitride, oxide, complex oxide, nitride oxide, carbide, sulfide, chloride, silicide, fluoride, boride, A thin film for a reflective film or transflective film in which a compound phase comprising at least one of hydride, phosphide, selenium, and tellurium is dispersed.

[2] As a compound phase, further, silver nitride, oxide, composite oxide, nitride oxide, carbide, sulfide, chloride, silicide, fluoride, boride, hydride, phosphide, 2. The thin film for a reflective film or transflective film according to claim 1, wherein at least one of selenide and tellurium is dispersed.

[3] The thin film according to claim 1 or 2, wherein the content of the compound phase is 0.001 to 2.5% by weight.

[4] The thin film according to claim 1 or 2, wherein the content of the compound phase is 0.001 to 1.0% by weight.

[5] The thin film according to claim 1 or 2, wherein the content of the compound phase is 0.001 to 0.5% by weight.

6. The reflective film according to any one of claims 1 to 5, wherein the matrix is a silver alloy, and the silver alloy is an alloy of silver and at least one of gallium, noradium, and copper. Or a thin film for a transflective film.

7. The thin film for a reflective film or transflective film according to claim 6, wherein the concentration of gallium, palladium and copper alloyed with silver is 0.01 to 10% by weight.

8. The thin film for a reflective film or a transflective film according to claim 6, wherein the concentration of gallium, palladium and copper alloyed with silver is 0.01 to 5% by weight.

9. The thin film for a reflective film or transflective film according to claim 6, wherein the concentration of gallium, palladium, and copper alloyed with silver is 0.01 to 3.5% by weight.

[10] In a matrix that also has silver or silver alloy strength, gallium, noradium, copper nitride, oxide, complex oxide, nitride oxide, carbide, sulfide, chloride, silicide, fluoride, boride, A sputtering target in which a compound phase composed of at least one of hydride, phosphide, selenium oxide, and tellurium oxide is dispersed.

[II] The compound phase is silver nitride, oxide, composite oxide, nitride oxide, carbide, sulfide, salt 11. The sputtering target according to claim 10, comprising at least one of oxides, silicides, fluorides, borides, hydrides, phosphides, selenides, and tellurides.

[12] The sputtering target according to claim 10 or 11, wherein the content of the compound phase is 0.001 to 2.5% by weight.

[13] The sputtering target according to claim 10 or 11, wherein the content of the compound phase is 0.001 to 1.0% by weight.

[14] The sputtering target according to claim 10 or 11, wherein the content of the compound phase is 0.001 to 0.5% by weight.

[15] The sputtering according to any one of claims 10 to 14, wherein the matrix is a silver alloy, and the silver alloy is an alloy of silver and at least one of gallium, palladium, and copper. target.

16. The sputtering target according to claim 15, wherein the concentration of gallium, palladium and copper alloyed with silver is 0.01 to 10% by weight.

17. The sputtering target according to claim 15, wherein the concentration of gallium, palladium and copper alloyed with silver is 0.01 to 5% by weight.

18. The concentration of gallium, palladium and copper alloyed with silver is 0.01 to 3.5% by weight.

5. The sputtering target according to 5.

[19] An optical recording medium comprising the thin film according to any one of claims 1 to 9 as a reflective film or a transflective film.